EP0079712A1 - In Borat-Lösung lösliche Polyvinylalkohol-Filme - Google Patents

In Borat-Lösung lösliche Polyvinylalkohol-Filme Download PDF

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Publication number
EP0079712A1
EP0079712A1 EP82305772A EP82305772A EP0079712A1 EP 0079712 A1 EP0079712 A1 EP 0079712A1 EP 82305772 A EP82305772 A EP 82305772A EP 82305772 A EP82305772 A EP 82305772A EP 0079712 A1 EP0079712 A1 EP 0079712A1
Authority
EP
European Patent Office
Prior art keywords
film
polyvinyl alcohol
acid
borate
molecular weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP82305772A
Other languages
English (en)
French (fr)
Other versions
EP0079712B2 (de
EP0079712B1 (de
Inventor
Edward J. Kaufmann
Barry A. Sudbury
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clorox Co
Original Assignee
Clorox Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=23244308&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0079712(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Clorox Co filed Critical Clorox Co
Priority to AT82305772T priority Critical patent/ATE34999T1/de
Publication of EP0079712A1 publication Critical patent/EP0079712A1/de
Application granted granted Critical
Publication of EP0079712B1 publication Critical patent/EP0079712B1/de
Publication of EP0079712B2 publication Critical patent/EP0079712B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the invention relates to polyvinyl alcohol films which are soluble in borate containing solutions and more particularly to such films in the form of envelopes containing laundry additives such as detergents and the like.
  • Methyl cellulose, polyethylene oxide and polyvinyl alcohol are particularly useful film materials of this nature.
  • Methyl cellulose films generally do not have sufficient solubility at higher water temperatures.
  • polyethylene oxide films tend to absorb moisture too readily and become tacky.
  • Polyvinyl alcohol films do not have the problems of methyl cellulose or polyethylene oxide films. However, when these films are placed in solutions containing borate at levels and pHs frequently encountered in laundry applications, the rate of solubility of such films is severely reduced. Yet, borate is often present in clothes washing liquors and the like, since one of the most widely used bleaching compositions is principally sodium perborate, which forms borate ions in solution. Other borate sources such as borax, are also often used as laundry additives.
  • the present invention is directed to overcoming the problem of slow dissolution rates of polyvinyl alcohol films in borate containing solutions as set forth above.
  • a polyvinyl alcohol film which is readily soluble in borate containing solutions.
  • the film comprises a composition selected from the group consisting of (a) a polyvinyl alcohol film having a number average molecular weight of no more than about 50,000; (b) a polyvinyl alcohol film containing a polyhydroxy compound (PHC) that has a binding constant, K 2 , with borate, in aqueous solution, K 2 being defined as equal to (Complex) , that is greater (borate) ( PHC ) 2 than about 800M -2 at 25°C; (c) a polyvinyl alcohol film containing an acid having an acid dissociation constant, in water at 25°C, greater than about 10 9M; and (d) mixtures thereof, the composition being selected such that 50% or more, by volume, of a 1.5cm x l.5cm x 0.0038cm piece of said film, when agitated in a volume of 750 cc of
  • a laundry additive combination in accordance with another embodiment of the present invention includes the laundry additive and a sealed envelope containing that additive.
  • the envelope is formed of a polyvinyl alcohol film, which film incorporates means for solubilizing the envelope sufficiently so that a piece of the film will dissolve when tested as previously set forth.
  • the present invention thus solves the problem of providing polyvinyl alcohol films which will rapidly dissolve in solutions which contain borate at levels and pHs normally encountered in laundry applications.
  • polyvinyl alcohol when used herein this term is meant to include the polyvinyl alcohol itself, derivatives thereof, and its water soluble copolymers.
  • the polyvinyl alcohol resins described herein are generally produced by the hydrolysis of polyvinyl acetate and generally have a degree of hydrolysis between about 70% and about 98%.
  • envelopes made of polyvinyl alcohol films can be used to enclose premeasured amounts of laundry additives such as detergents, bleaches, brighteners, builders, fabric softeners, and the like.
  • Such polyvinyl alcohol films are generally formed from polyvinyl alcohol resins of a desired degree of hydrolysis.
  • the polyvinyl alcohol is dissolved in water, with heating, and one or another conventional plasticizers, such as, for example, polyethylene glycol having a molecular weight of 200 to 600, release agents, and an anti-blocking agent, if desired, are also dissolved in the same solution. Thereafter, the solution is simply cast and the water evaporated to produce a film with the desired physical properties.
  • the conventional polyvinyl alcohol films of the prior art have very adequate solubility in water. However, when there is a significant borate concentration in the water and when the pH is that frequently encountered in washing liquors, such polyvinyl alcohol films will not dissolve sufficiently readily to deliver a laundry additive to the solution early in the wash cycle.
  • Mild agitation is defined, for the purposes of the test, as agitation in a volume of 750cc of the solution in a cylindrical container 9.5cm in diameter using an oblong magnetic stirring rod about lcm x 5cm at a speed sufficient to cause a vortex to extend about 20% of the way downwardly from the surface of the solution.
  • the first composition which satisfies the test is a polyvinyl alcohol film produced from polyvinyl alcohol resins characterized by having a number average molecular weight below about 50,000, more preferably below about 25,000, and still more preferably of about 10,000.
  • this first composition is utilized without any of the second or third compositions set out below, at least about 50% of the polyvinyl alcohol resin on which the film is based must consist of a polyvinyl alcohol of such an average molecular weight, more preferably at least about 80% and still more preferably about 100%.
  • a second composition which will satisfy the above test, either by itself or in combination with the first constituent or the third constituent which will be set out below, or with both the first and third constituents, is a polyvinyl alcohol film which contains a polyhydroxy compound (PHC) which has a binding constant with borate in aqueous solutions (K 2 ) as defined by the equation that is greater than about 800 M -2 at 25°C; the constituents concentrations being in moles per liter.
  • PLC polyhydroxy compound
  • Particularly useful polyhydroxy compounds are levulose (fructose), mannitol, catechol, sorbitol, sorbose, pentaerythritol and meso-erythritol.
  • the polyhydroxy compound is utilized by itself to solubilize the polyvinyl alcohol film, it is preferably present in an amount of at least about 10 % , by weight, of the polyvinyl alcohol film, the effective amount depending on the identity of the polyhydroxy compound.
  • lesser amounts of the polyhydroxy compound can be utilized if the film includes a polyvinyl alcohol having a relatively lower molecular weight, for example, a number average molecular weight below about 50,000, or if the film includes an acid as will be set out below.
  • a third polyvinyl alcohol film having the desired characteristics is one which contains an organic, inorganic or polymeric acid having an acid dissociation constant, in water at 25°C, greater than about 10 -9 M and preferably greater than about 10 M.
  • Polyacrylic acids with average molecular weights in the range from about 3000 to about 150,000 are very useful acids for such purposes.
  • Other acids are also useful, for example, citric acid, succinic acid, tartaric acid, potassium hydrogen phthalate, sodium dihydrogen phosphate, adipic acid, cysteine, glutamic acid, benzoic acid and oxalic acid.
  • the acid when utilized by itself, it is preferred that it be in a concentration of at least about 10%, by weight, based on the weight of the polyvinyl alcohol film.
  • the amount of acid can be reduced if some polyhydroxy compound, as set out above, is present and/or if the film includes polyvinyl alcohol having a number average molecular weight below about 50,000 and more preferably below about 25,000.
  • the polyvinyl alcohol film in accordance with the present invention, be capable of satisfying the objective test of solubility in a borate containing solution and at a pH as set out above.
  • detergents are enclosed in envelopes in accordance with the present invention, but also builders, bleaches, brighteners, fabric softeners, anti- soiling polymers and other laundry additives may be so enclosed, provided they do not dissolve or otherwise interact deleteriously with the film material.
  • 70% of the film dissolved in 300 seconds.
  • polyhydroxy compounds should have K 2 values greater than about 800M to provide a film that meets desired solubility criteria.
  • a polyvinyl alcohol film of number average molecular weight greater than 50,000 has been shown to be rapidly soluble due to the inclusion of these polyhydroxy compounds having K 2 greater than 800.
  • polyvinyl alcohol resins of as much as 200,000 number average molecular weight are expected to be rendered rapidly soluble by the correct choice of polyhydroxy compounds and its level in the film.
  • This procedure yielded a film 0.0038cm thick containing approximately 66% polyvinyl alcohol, 24 % polyacrylic acid, 5 % polyethylene glycol and 5 % water. Using the evaluation procedure as set out above, >95% of the film dissolved in 150 seconds.
  • solubility characteristics can become important when the laundry additive combination comprising a laundry additive and an envelope made from a film as set forth herein is used in extreme or misuse conditions. For example, it is not uncommon for the consumer to use more than the recommended amount of bleaching compositions containing sodium perborate when laundering a heavily soiled load or in small volumes of washing liquor. Such would result in a concentration of borate as high as 3.4 x 10 M or even higher in the laundry liquor. Also, it is not uncommon for the consumer to launder delicate items at temperatures significantly less than 37.5°C. Both conditions can have the effect of reducing the solubility rate of films that meet the criteria set forth previously herein.
  • Example 29 in which one of the embodiments of this invention is used (low molecular weight), has an acceptable solubility rate under the conditions set forth in this example, the solubility rate is relatively low.
  • the embodiments which teach the use of polyvinyl alcohol resins with number average molecular weight of about 50,000 or less, and the use of a polyhydroxy compound which has a binding constant with borate above about 800 M -2 a film is produced with a solubility rate considerably higher and more acceptable than that of Example 29.
  • the combinations of the embodiments presented herein offers significant advantages over separate use of the individual embodiments. It can be expected that combinations of any two of the particular embodiments presented herein, or combinations of all three embodiments, will yield films that readily meet solubility criteria set forth previously.
  • the present invention is directed to and discloses both a polyvinyl alcohol film and a laundry additive-envelope combination with the film being of proper solubility rate in borate containing solutions under normal laundry conditions so as to deliver the contents of an envelope made of the film early during a wash cycle, even when borate is present.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Detergent Compositions (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP82305772A 1981-11-10 1982-10-29 In Borat-Lösung lösliche Polyvinylalkohol-Filme Expired - Lifetime EP0079712B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82305772T ATE34999T1 (de) 1981-11-10 1982-10-29 In borat-loesung loesliche polyvinylalkohol-filme.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US31996681A 1981-11-10 1981-11-10
US319966 1981-11-10

Publications (3)

Publication Number Publication Date
EP0079712A1 true EP0079712A1 (de) 1983-05-25
EP0079712B1 EP0079712B1 (de) 1988-06-08
EP0079712B2 EP0079712B2 (de) 1993-10-06

Family

ID=23244308

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82305772A Expired - Lifetime EP0079712B2 (de) 1981-11-10 1982-10-29 In Borat-Lösung lösliche Polyvinylalkohol-Filme

Country Status (10)

Country Link
EP (1) EP0079712B2 (de)
JP (1) JPS5887145A (de)
AT (1) ATE34999T1 (de)
AU (2) AU565500B2 (de)
BR (1) BR8206469A (de)
CA (1) CA1230795A (de)
DE (1) DE3278638D1 (de)
ES (1) ES8401553A1 (de)
GR (1) GR77732B (de)
MX (2) MX165884B (de)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0160254A2 (de) * 1984-04-28 1985-11-06 Henkel Kommanditgesellschaft auf Aktien Waschzusatz
EP0164703A2 (de) * 1984-06-14 1985-12-18 Henkel Kommanditgesellschaft auf Aktien Waschzusatz
EP0234867A2 (de) * 1986-02-20 1987-09-02 The Clorox Company Konzentrierte, phosphatfreie Reinigungsmittelpasten
US4747976A (en) * 1987-05-14 1988-05-31 The Clorox Company PVA films with nonhydrolyzable anionic comonomers for packaging detergents
EP0291198A2 (de) * 1987-05-14 1988-11-17 The Clorox Company Folien aus mit nicht hydrolysierbaren anionischen Comonomeren modifizierten PVA,die Additive enthalten
US4801636A (en) * 1987-03-24 1989-01-31 The Clorox Company Rinse soluble polymer film composition for wash additives
WO1990012864A1 (en) * 1989-04-24 1990-11-01 Unilever Nv Packaged liquid cleaning product
US4972017A (en) * 1987-03-24 1990-11-20 The Clorox Company Rinse soluble polymer film composition for wash additives
EP0407301A1 (de) * 1989-07-05 1991-01-09 Nln Sa Polyvinylalkoholfilm mit verbesserter Lösbarkeit
GB2244220A (en) * 1990-05-01 1991-11-27 Courtaulds Films & Packaging Packaging materials
EP0524823A3 (en) * 1991-07-26 1993-05-05 Kureha Chemical Industry Co., Ltd. A resin composition and food packaging materials formed therefrom
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
US6281183B1 (en) 1999-03-17 2001-08-28 Unilever Home & Personal Care, Division Of Conopco, Inc. Process for producing a water soluble package
US6363693B1 (en) 1999-03-17 2002-04-02 Unilever Home & Personal Care, Usa Process for producing a water soluble package
US6378274B1 (en) * 1999-03-17 2002-04-30 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Process for producing a water soluble package
US6451750B2 (en) 2000-04-14 2002-09-17 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Water soluble package and liquid contents thereof
US6479448B2 (en) 2000-05-15 2002-11-12 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Liquid detergent composition
US6699826B1 (en) 1998-07-23 2004-03-02 Kao Corporation Sheet-form laundering article
EP1418196A1 (de) * 2002-11-11 2004-05-12 The Nippon Synthetic Chemical Industry Co., Ltd. Wasserlöslicher Film
US7674761B2 (en) 2001-03-16 2010-03-09 Unilever Home & Personal Care, Division Of Conopco, Inc. Water soluble sachet with a dishwashing enhancing particle

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6157700A (ja) * 1984-08-29 1986-03-24 花王株式会社 水溶性フイルムを用いた単位包装洗剤製品
ATE121128T1 (de) * 1991-05-14 1995-04-15 Ecolab Inc Zweiteiliges chemisches konzentrat.
JP3561572B2 (ja) * 1996-04-03 2004-09-02 信越ポリマー株式会社 ポリビニルアルコール系樹脂組成物
JP3609898B2 (ja) * 1996-06-03 2005-01-12 株式会社クラレ 薬剤包装用水溶性フィルム
JPH10324785A (ja) * 1997-05-27 1998-12-08 Kuraray Co Ltd ビニルアルコール系重合体組成物
GB0222964D0 (en) 2002-10-03 2002-11-13 Unilever Plc Polymeric film for water soluble package
WO2017043507A1 (ja) * 2015-09-11 2017-03-16 日本合成化学工業株式会社 水溶性フィルムおよびそれを用いた薬剤包装体、並びに水溶性フィルムの製造方法
CN108779274B (zh) 2016-04-13 2022-08-09 蒙诺苏尔有限公司 水溶性膜、采用所述膜的包以及其制造和使用方法
WO2017218414A1 (en) 2016-06-13 2017-12-21 Monosol, Llc Use of a first film and a second film to improve seal strength of a water-soluble
CN109311574A (zh) * 2016-06-13 2019-02-05 蒙诺苏尔有限公司 水溶性小包装
US10443024B2 (en) 2016-06-13 2019-10-15 Monosol, Llc Water-soluble unit dose articles made from a combination of different films
US10611988B2 (en) 2017-03-16 2020-04-07 The Procter & Gamble Company Methods for making encapsulate-containing product compositions
US10385296B2 (en) 2017-03-16 2019-08-20 The Procter & Gamble Company Methods for making encapsulate-containing product compositions
US10385297B2 (en) 2017-03-16 2019-08-20 The Procter & Gamble Company Methods for making encapsulate-containing product compositions
US11441002B2 (en) * 2017-05-31 2022-09-13 Rohm And Haas Company Free standing dispersant film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4082678A (en) * 1976-11-10 1978-04-04 The Procter & Gamble Company Fabric conditioning articles and process
DE2919886A1 (de) * 1978-05-18 1979-11-22 Unilease S A Verfahren zur reinhaltung von verschmutzungsgefaehrdeten innen- und aussenoberflaechen
EP0011502A1 (de) * 1978-11-17 1980-05-28 Unilever Plc In einem geschlossenen Sack aus folienartigem Material enthaltene körnige Waschmittelzusammensetzung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB927963A (en) * 1961-01-06 1963-06-06 Kurashiki Rayon Kk Method of preventing water-soluble films of polyvinyl alcohol derivatives from adhering and non-sticky films made thereby
US3220991A (en) * 1962-03-28 1965-11-30 Monsanto Co Heat stabilization of polyvinyl alcohol with aliphatic polycarboxylic acid
AU508381B2 (en) * 1974-01-03 1980-03-20 E. X. Dupont De Nemours and Company Water soluble films

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4082678A (en) * 1976-11-10 1978-04-04 The Procter & Gamble Company Fabric conditioning articles and process
DE2919886A1 (de) * 1978-05-18 1979-11-22 Unilease S A Verfahren zur reinhaltung von verschmutzungsgefaehrdeten innen- und aussenoberflaechen
EP0011502A1 (de) * 1978-11-17 1980-05-28 Unilever Plc In einem geschlossenen Sack aus folienartigem Material enthaltene körnige Waschmittelzusammensetzung

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4743394A (en) * 1984-03-23 1988-05-10 Kaufmann Edward J Concentrated non-phosphate detergent paste compositions
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
EP0160254A3 (en) * 1984-04-28 1986-03-26 Henkel Kommanditgesellschaft Auf Aktien Additive for a washing bath
US4610799A (en) * 1984-04-28 1986-09-09 Henkel Kommanditgesellschaft Auf Aktien Washing additive in paste form containing an activator for per compounds, and package therefor
EP0160254A2 (de) * 1984-04-28 1985-11-06 Henkel Kommanditgesellschaft auf Aktien Waschzusatz
EP0164703A2 (de) * 1984-06-14 1985-12-18 Henkel Kommanditgesellschaft auf Aktien Waschzusatz
EP0164703A3 (en) * 1984-06-14 1986-04-02 Henkel Kommanditgesellschaft Auf Aktien Additive for washing
EP0234867A2 (de) * 1986-02-20 1987-09-02 The Clorox Company Konzentrierte, phosphatfreie Reinigungsmittelpasten
EP0234867A3 (en) * 1986-02-20 1989-04-26 The Clorox Company Concentrated non-phosphate detergent paste compositions
US4972017A (en) * 1987-03-24 1990-11-20 The Clorox Company Rinse soluble polymer film composition for wash additives
US4801636A (en) * 1987-03-24 1989-01-31 The Clorox Company Rinse soluble polymer film composition for wash additives
USRE34988E (en) * 1987-05-14 1995-07-04 The Clorox Company Films from PVA modified with nonhydrolyzable anionic comonomers
EP0291198A2 (de) * 1987-05-14 1988-11-17 The Clorox Company Folien aus mit nicht hydrolysierbaren anionischen Comonomeren modifizierten PVA,die Additive enthalten
US4885105A (en) * 1987-05-14 1989-12-05 The Clorox Company Films from PVA modified with nonhydrolyzable anionic comonomers
EP0291198A3 (en) * 1987-05-14 1990-03-28 The Clorox Company Films from pva modified with nonhydrolyzable anionic comonomers in the form of pouches containing cleaning compositions
US4747976A (en) * 1987-05-14 1988-05-31 The Clorox Company PVA films with nonhydrolyzable anionic comonomers for packaging detergents
WO1990012864A1 (en) * 1989-04-24 1990-11-01 Unilever Nv Packaged liquid cleaning product
EP0407301A1 (de) * 1989-07-05 1991-01-09 Nln Sa Polyvinylalkoholfilm mit verbesserter Lösbarkeit
FR2649403A1 (fr) * 1989-07-05 1991-01-11 Lenigen Norbert Film d'alcool polyvinylique ayant des caracteristiques ameliorees de solubilite
GB2244220A (en) * 1990-05-01 1991-11-27 Courtaulds Films & Packaging Packaging materials
GB2244220B (en) * 1990-05-01 1994-10-12 Courtaulds Films & Packaging Packaging materials
US5389425A (en) * 1990-05-01 1995-02-14 Courtaulds Packaging Limited Packaging materials
US5318812A (en) * 1991-07-26 1994-06-07 Kureha Chemical Industry Company, Ltd. Resin composition and food packaging materials formed therefrom
US5270372A (en) * 1991-07-26 1993-12-14 Kureha Chemical Industry Co., Ltd. Resin composition and food packaging materials formed therefrom
EP0524823A3 (en) * 1991-07-26 1993-05-05 Kureha Chemical Industry Co., Ltd. A resin composition and food packaging materials formed therefrom
US6699826B1 (en) 1998-07-23 2004-03-02 Kao Corporation Sheet-form laundering article
US6363693B1 (en) 1999-03-17 2002-04-02 Unilever Home & Personal Care, Usa Process for producing a water soluble package
US6378274B1 (en) * 1999-03-17 2002-04-30 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Process for producing a water soluble package
US6281183B1 (en) 1999-03-17 2001-08-28 Unilever Home & Personal Care, Division Of Conopco, Inc. Process for producing a water soluble package
US6451750B2 (en) 2000-04-14 2002-09-17 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Water soluble package and liquid contents thereof
US6479448B2 (en) 2000-05-15 2002-11-12 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Liquid detergent composition
US7674761B2 (en) 2001-03-16 2010-03-09 Unilever Home & Personal Care, Division Of Conopco, Inc. Water soluble sachet with a dishwashing enhancing particle
US8367599B2 (en) 2001-03-16 2013-02-05 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Dishwashing composition with particles
EP1418196A1 (de) * 2002-11-11 2004-05-12 The Nippon Synthetic Chemical Industry Co., Ltd. Wasserlöslicher Film
US7067575B2 (en) 2002-11-11 2006-06-27 The Nippon Synthetic Chemical Industry Co., Ltd. Water-soluble film of polyvinyl alcohol

Also Published As

Publication number Publication date
JPH0370760B2 (de) 1991-11-08
GR77732B (de) 1984-09-25
CA1230795A (en) 1987-12-29
JPS5887145A (ja) 1983-05-24
AU597328B2 (en) 1990-05-31
ES517586A0 (es) 1983-12-16
AU565500B2 (en) 1987-09-17
AU9021582A (en) 1983-05-19
DE3278638D1 (en) 1988-07-14
ES8401553A1 (es) 1983-12-16
ATE34999T1 (de) 1988-06-15
EP0079712B2 (de) 1993-10-06
AU6767987A (en) 1987-06-25
MX9206308A (es) 1994-05-31
BR8206469A (pt) 1983-09-27
EP0079712B1 (de) 1988-06-08
MX165884B (es) 1992-12-07

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